Electrodeposition of nickel



l'at ented Apr. 14, 1959 2,882,208 ELECTRODEPOSITION OF NICKEL Donald H.Becking, Birmingham, Richard J. Clauss, Grosse Pointe Park, and HenryBrown, Huntington Woods, Mich., assignors to The Udylite Research Cor-jporation, Detroit, Mich., a corporation of Michigan No Drawing.Application September 23, 1957 Serial No. 685,417

14 Claims. (Cl. 204-49) In accordance with thisinvention, it has beenfound that certain unsaturated organic compounds containing both thetriple bonded C-=-C-unsaturated group and the triple bonded unsaturatedCEN group in the same molecule, as exemplified by the compounds of TableI, give brilliant ductile plate when used in aqueous acidic nickel bathsin unusually small concentrations in conjunction with the'well-knownorganic .sulfon-compounds as exemplified in Table II.

While it is old to use compounds containing/the cyano group (nitriles),(US. Patent 2,524,010, September 26, 1950), in conjunctionwith theorganic sulfoncompounds, nevertheless the concentrations necessary toobtain bright plate have been between 0.1 gram to 1 gram per liter. Ithas been found that on continued electrolysis of nickel baths usingconcentrations of 0.1 g./l.- to 1 g./l. of cyano compounds suchascyanoacetamide, lactonitrile, etc. not containing a sulfonic acid, inthe same molecule, that there accumulates hydrolytic and electrolyticdegradation products which cause increasing brittleness in the bath withthe continued additions necessary to maintain brightness duringcontinuous plating. It has also been found that the harmful break-downproducts formed during continuous electrolysis in the case of suchaliphatic nitriles as cyanoacetamide, lactonitrile and others are notreadily removed by activated carbon or absorptive clays, and the nickelbaths give increasingly brittle plate andbecome exceedingly difiicult topurify. These serious embrittling defects are not encountered with thecompounds of Table I which contain both the C z -N and CEC-unsaturatedgroups. It Will be noted that in each of the compounds of Table I, theCEN group is separated by an ether linkage from the CEC group. Thislinkage is considered to be an important contributor ot theeffectiveness of these compounds. The concentrations that are necessaryfor high brilliance without excessive brittleness are very low, 0.001 to0.01 gram per liter, much lower than the recommended concentrations forcompounds carrying' separately either the -CEC-gro-up or the -CEN group.The presence of both types of triple bonds in the same molecule exertsan enhanced brightening effect over either one alone.

The compounds of Table. I are preferably used in concentrations of 0.001to 0.005 gram/liter in conjunction with the organic sulfon-compoundsillustratedin Table II. The compounds of Table I can be used inconjunction with other nickel brighteners such as those I containing thebond (U.S. Patent 2,647,866, August 4, 1953), u ing lower concentrationsof the compounds ofrTable I to- :gether with lower concentrations of pa-.. compounds giving improved results.

TABLE I Optimum Cone, grams/liter E (1) I'iozo-o-o CYZHACEN 0. 001-0.005

3-(beta-cyanoethoxy)-3-rnethyl-butyne-1 e (-2) HCEO(l1-O C2H40 C2H4CEN0. 001-0. 008

. em (s) Ho5ceo 0113.0 0.1140 onncEN 0. 001-0. 008

CH: I

'CzHs I 4 HCECCO C2H4CEN 0. 001-0. 005

( s Bozo-c1120 CzHtCEN 0. 001-0. 003 (6) HCEC-CH2O CZHJO ORHACEN 0.001-0. 005

HCEC(IJ--O 021140 021340 CzH4CEN I CH3 w (8 HCEC-(f-OCzEQCEN.0.001-0.005

CHzOCHtCEC-CHzOCzHtOEN 0.001-0.01 (10) HOCHr-CECCH2OC2H4CEN (1003-0015(11) NEC-GzHiOHzCCEOCHzO CzH CEN 0. 001-0. 01

TABLE II 0 timum Sulfur-Containing Brighteners one grams/liter Benzenesulfonamide 0.1-3 Toluenesulionamides (oand p- 0. 1-2 o-Benzoylsu1fimide 0.1-2 N-Benzoyl benzene sulfonimide 0.1-1 p-Toluenesulfonch10ran1ide. 0. 1-1 p-Brom benzene sulfonamide- 0.1-1 6 Chlor obenzoy1 sulfimide. 0.1-1 m-Aldehydo benzene sulfonamide 0. 1-1Sulfomethyl benzene sulfonamide 0. 1-6 Benzene sulfonamide m-carboxylicami e. 0. 1-3 7-Aldehydo o-benzoyl sulfimide 0. 1-3 N-acetyl benzenesulfonimide. 0. 1-2 Methoxy benzene sulfonamides 0.1-1 Hydroxymethylbenzene sultona 0. 1-2 Allyl sultonamide 0, 4-12 Benzene sulionic acids(mono-, di 1-15 p-Brorn benzene sulfonic acid 3-6 'Benzaldehyde sulfonieacids (0, m, p) 2-0 Diphenyl sulfone sulfonic acid 1-8 Naphthalenesulfonic acids (mono-, di-, and tri-) 1-8 Benzene sulfohydroxarnic acid1-5 p-Chlor benzene sulfonic acid' 1-15 Diphenyl sulfonic acid- 1-5m-Diphenyl benzene sulfonic acid. l-4 2-Chloro-5-sul1obenzaldehyde 1-5m-Benzene disulfonamide- 0. 5-1 Allyl,su.lfonic acid 0. 4-12Dichlorobenzene sultonic acids" 0.5-8 .Dibenzene sulf0nimide 0. 1-3Di-toluene sulfonimide--. 0. 1-3 Z-Bntyne-l, 4-disu1ionic ac 5-204-Hydr0xy-2-butyne-1-sulton 0. 2-2 2 Butyne-l-sultonic acid 0 05-1. 5 3Oh1or0-2-propyne-1-sulfoni 0 05-1. 6 2-butene-L4-disulfonic acid-.. 03-52-chloro butene-4-sult'onic acid 0.3-5 2-chloro propene sulfonic acid 0.1-1. 5 Cinnamyl sulionic acid 0. 1-3. 0 3-1henyl-2-propyne-l-sulfonicacid. 0. 3-3. 0 4-Methoxy-2-butyne-1-sulionic acid 0. 2-2

The more rapid the rate of cathode or solution agitation, the lower theconcentration of the compounds of Table I that are necessary for highbrilliance. For example, with strong air agitation of the bath, thelower concentrations of the compounds of Table I are used.

The combination of the compounds of Table I with those of Table II canbe used in all types of acidic nickel baths that give good ductile graynickel deposits, such as Watts nickel baths, high chloride, fluoborate,and sulfamate baths and mixtures of these various nickel salts. Sodium,potassium, and lithium ions may be pres- 'ent, also ammonium ions,though the latter should prefferably be kept below about 7 grams/literfor maximum ductility and brightness. Boric acid is the preferredbuffer.

The best pH range is from about 2.8 to 4.5, though pH values of 2 to 6may be used. The temperature of the bath may be from room to 190 F.,though in general 120 F. to 160 F. is preferred.

When no air agitation or strong mechanical or hydraulie agitation isused, it is preferred to use a suitable surface-active agent such assodium lauryl sulfate, sodium 2-ethyl 'hexyl sulfate or sul'fonate,octyl sulfonic acid, etc., to prevent gas-pitting. With air agitation asurface active agent such as sodium 2-ethyl hexyl sulfate or' sulfonatecan be used which does not foam excessively, or else an anti-foam suchas a silicone oil can be used with a more powerful sm'face-ac'tiveagent, such as sodium lauryl sulfate.

The preferred organic sulfon-compounds to be used with the compounds ofTable I are o-benzoyl sulfimide and the benzene sulfonamides andsulfonimides (0.1 gram/liter 'to saturation) especially when used inconjunction with allyl 'sul-fonic acid (0.6-2 grams per liter) or2-butyne-1,4-disulfonic acid (2-10 grams/liter).

In the following examples typical bath compositions and conditions areillustrated for obtaining the bright nickel deposits in accordance withthis invention, but it is to be understood that they are representativeonly, and that the compounds of Table I can be used in such bathcompositions in combination with each compound or combinations of thecompounds of Table II or other organic Stilton-compounds similar tothose of Table II such V H M smmmOO- O in the approximate -proportionsindicated in Table II.

Example A Grams/liter NiSO .6H O 200-300 NiCl .6H O 30-80 130 so-soNaBFd I 0-015 Example 1 of Table I: 3-{beta cyano'ethoxy)- p n3-methyl-butyne-l 0.001-0.004 Sodium allyl sulfonate 0.6-2 Benzenesulfonamide 1-"2 o-Benzoyl sulfiinide j Temperature, 120 F.-1,60 F. pH,3.2-4.8.

Example B Y I Grant /liter 'NiCl jH Q 100-200 NiSO .6H O H3BO3 Example 2of Table I 0002-0005 Sodium allyl sulfonate 0.6-2 oBenzoyl sulfimide 1-2Beniene sulfonamide 1-2 Temperature, 120 F.-160 F. pH, 3.2-4.8.

4 Example C Grams/liter NiSO .6H O 200-300 NiC1 .6H O 30-100 H BO 30-50Example 10 of Table I 0.005-0015 2-butyne-1,4-disulfonic acid (Na, K orNi Temperature, F.- F. pH, 3.2 to 4.8.

The above baths give brilliant ductile nickel deposits with very goodrate of brightening or leveling.

What is claimed is:

'1. A bath for electrodepositing bright, ductile nickel plate whichcomprises an aqueous acidic solution containing -at least oneelectrolyte selected from the group consisting of nickel sulfate, nickelchloride, nickel fluoborate and nickel s'ulfamate, and having dissolvedtherein about 0.1 gram/liter to saturation of at least one organicsulfoncompound selected from the class consisting of benzene, biphenylandnaphthalene 'sulfonic acids, sulfonamides and sulfonirni'des and themixed phenyl, biphenyl and naphthyl stilfonamides and the mono-, di-,tri-, and tetra-sulfo'nimid'es thereof, and dibenzene sulfonimides andthe halogen, methyl, and aldehydo derivatives of said sulfonic acids,sulfonamides and sulfonimides, and beta unsaturated alkene and alkynesulrfonic acids having 4-2 carbon atoms, and about 0.001 to about 0.015gram/liter of a nitrile having the elements hydrogen, nitrogen, oxyg'en'and 6-1-7 carbon atoms inclusive and containing a -;CC group, which CECgroup is separated from the -C-EN group by at least one ether linkage.

'2. A bath in accordance with claim 1 wherein the said nitrile thecompound and is present in a concentration in the bath of 0.001 to about0.008 gram/liter. 3. A bath in accordance with claim 1 wherein the saiduitrile is the compound OH] 'SHCEC- -li-OtZiEO'N ahdis dissolved'in thesaid nickel bath in a concentration at 0.001 to about 0.01-gram/liter. V,-4.'A bath in accordance with claim 1 wherein the said nitrile is thecompound HCECCH 0C H CN and is dissolved in the said nickel bath in aconcentration of 0.001 to about 0.01 gram/liter.

55A bath in accordance with claim 1 wherein said organic sulfon-compoundis allyl sulfonate.

6. A bath in accordance with claim 1 wherein said organicsulfon-compound is 2-butyne-l,4-disulfonate.

7 A method of electrodepositing bright, ductile nickel plate whichcomprises 'electrolyz'ing an aqueous acidic solution comprising at leastone nickel salt selected from the group consisting of nickel sulfate,nickel chloride, nickel fiuoborate and nickel sulfamate, said bathcontaining dissolved therein about 0.1 gram/liter to saturation of atleast one organic sulfon-compound selected from the group consisting ofbenzene, biphenyl and naphthalene sulfonic acids, sulfonamides andsulfonimides and the mixed phenyl, biphenyl and naphthyl sulfonamidesand the mono-, di-, tri-, and tetra-sulfonimides thereof, and dibenzenesulfonimides and the halogen, methyl, and aldehydo derivatives of saidsulfonic acids, sulfonamides and sulfonimides, and beta unsaturatedalkene and alkyne sulfonic acids having 4-2 carbon atoms, and about0.001 to about 0.015 gram/ liter of a nitrile having the elementshydrogen, nitrogen, oxygen and 6-17 carbon atoms inclusive andcontaining a CEC group, which CEC group is separated from the CEN groupby at least one ether linkage.

8. A method in accordance with claim 7 wherein the said nitrile is thecompound and is present in a concentration in the bath of 0.001 to about0.008 gram/liter.

9. A method in accordance with claim 7 wherein the said nitrile is thecompound 6 and is present in the said nickel bath in a concentration of0.001 to about 0.01 gram/liter.

10. A method in accordance with claim 7 wherein the said nitrile is thecompound I-ICECCH OC H CN and is present in the said nickel bath in aconcentration of 0.001 to about 0.01 gram/liter.

11. A method in accordance with claim 7 wherein said organicsulfon-compound is allyl sulfonate.

12. A method in accordance with claim 7 wherein said organicsulfon-compound is Z-butyne-l,4-disulfonate.

13. A bath in accordance with claim 1 wherein the said nitrile is thecompound N E CC2H4OH2CC E and is present in a concentration in the bathof about 0.001 to about 0.01 gram/liter.

14. A method in accordance with claim 7 wherein the said nitrile is thecompound Du Rose et a1 Sept. 26, 1950 Brown July 23, 1957

1. A BATH FOR ELECTRODEPOSITING BRIGHT, DUCTILE NICKEL PLATE WHICHCOMPRISES AN AQUEOUS ACIDIC SOLUTION CONTAINING AT LEAST ONEELECTROLYTESELECTED FROM THE GROUP CONSISTING OF NICKEL SULFATE, NICKELCHLORIDE, NICKEL FLUOBORATE AND NICKEL SULFAMATE, AND HAVING DISSOLVEDTHEREIN ABOUT 0.1 GRAM/LITER TO SATURATION OF AT LEAST ONE ORGANICSULFONCOMPOUND SELECTED FROM THE CLASS CONSISTING OF BENZENE, BIPHENYLAND NAHTHALENE SULFONIC ACIDS, SULFONAMIDES AND SULFONIMIDES AND THEMIXED PHENYL, BIPHENYL AND NAPHTHYL SULFONAMIDES AND THE MONO-, DI-,TRI-, AND TETRA-SULFONIMIDES THEREOF, AND DIBENZENE SULFONIMIDES, ANDTHE HALOGEN METHYL, AND ALDEHYDO DERIVATIVES OF SAID SULFONIC ACIDS,SULFONAMIDES AND SULFONIMIDES, AND BETA UNSATURATED ALKENE AND ALKYNESULFONIC ACIDS HAVING 4-2 CARBON ATOMS, AND ABOUT 0.001 TO ABOUT 0.015GRAM/LITER OF A NITRILE HAVING THE ELEMENTS HYDROGEN, NITROGEN, OXYGENAND 6-17 CARBON ATOMS INCLUSIVE AND CONTAINING A -C$C GROUP, WHICH -C$CGROUP IS SEPARATED FROM THE -C$N GROUP BY AT LEAST ONE ETHER LINKAGE.